Study Into Alternative (Biobased) Polar Aprotic Solvents

Total Page:16

File Type:pdf, Size:1020Kb

Study Into Alternative (Biobased) Polar Aprotic Solvents Study into alternative (biobased) polar aprotic solvents Dr. Daan S. van Es Report 1742 Colophon Title Study into alternative (biobased) polar aprotic solvents Author(s) Dr. Daan S. van Es Number 1742 ISBN-number - Date of publication November 20th, 2017 Version End version Confidentiality yes OPD code - Approved by Dr. J. van Haveren Review Internal Name reviewer - Sponsor Ministry of Infrastructure and the Environment Client National Institute for Public Health and the Environment (RIVM) Wageningen Food & Biobased Research P.O. Box 17 NL-6700 AA Wageningen Tel: +31 (0)317 480 084 E-mail: [email protected] Internet: www.wur.nl/foodandbiobased-research © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research All rights reserved. No part of this publication may be reproduced, stored in a retrieval system of any nature, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of the publisher. The publisher does not accept any liability for inaccuracies in this report. 2 © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research Executive Summary This report is the second part of the project ‘Verkenning aprotische oplosmiddelen’. The goal of this project, which is a collaboration between Wageningen Food and Biobased Research (WFBR) and the National Institute for Public Health and the Environment (RIVM), is to identify new biobased alternatives to the currently disputed polar aprotic solvents (PAS) NMP, DMAc and DMF, which are suspected to be reprotoxic. The first objective of this desk study is to present an overview of both emerging and existing biobased chemicals (and materials), and to identify potential (side) streams of ‘new’ biobased chemicals that will (need to) be valorised in the near future. The description ‘new’ biobased chemicals relates to the fact that these substances are not (yet) commercially available in significant quantities, despite the fact that many of them have been known for more than a century. For example, substances like ethanol, lactic acid and citric acid are not considered new as they have already been produced by industrial scale fermentation for a long time. Furthermore, chemicals like bio succinic acid are not considered new, as they are currently still mostly produced from petrochemical feedstocks. Examples of substances that are considered as new in this study are for instance furandicarboxylic acid, levulinic acid and itaconic acid. While the information thus obtained is already interesting by itself from a regulatory perspective, the second objective of this study is to evaluate the replacement potential of these new biobased substances with regard to the PAS NMP, DMAc and DMF. Since many biobased chemicals are (highly) polar, the increasing availability of ‘new’ substances with unique chemical structures and properties could be the solution to finding safe alternatives to disputed PAS. For most of the existing and emerging biobased product streams ‘new’ substances have been identified, which has resulted in a list of substances (or classes of substances) that are likely to reach a significant production volume in the coming decades. This list has been prioritised according to criteria like feedstock availability, level of (industrial) development, whether or not a substance is already commercially produced, and its potential as alternative polar aprotic solvent. Based on these criteria, nineteen substances and substance classes have been identified as potential alternatives for the currently disputed PAS. Toxicological analysis should give more insight into the feasibility of these substances as safe alternatives for the currently disputed polar aprotic solvents. Next, the technical and economic feasibility should be determined for these substances in various key applications by the relevant stakeholders (industry, knowledge institutes, government). This also implies that synthesis and production of substances that are not yet readily available should be developed further. Due to the rather diffuse nature of the solvents market, with both many (potential) producers and end- © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research 3 users, as well as a myriad of applications, a proactive role of the government in stimulating and facilitating the development of these new biobased solvents and chemicals is strongly advised. Next to e.g. matchmaking events and ‘green deals’, a specific R&D program involving a broad number of stakeholders, (potential) solvent producers and users, and knowledge institutes (comparable to e.g. the Biobased Performance Materials program) is recommended in order to accelerate the introduction and acceptance of new, safe biobased solvents. 4 © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research Content Executive Summary 3 1 Introduction 6 2 Methods & Terminology 8 3 Results & Discussion 10 3.1 Biobased resources and chemicals 10 3.2 Glucose derived acids 11 3.3 Sugar derived alcohols 13 3.4 Hexose derived furanics and aromatics 15 3.5 Pentose derived furanics and aromatics 18 3.6 Uronic acids and derivatives 20 3.7 Glycerol and oleochemicals 21 3.8 Lignin derived chemicals 24 3.9 Terpenes and derivatives 26 3.10 Miscellaneous 27 3.11 Comparison with DOE list of top value added chemicals from biomass. 28 4 Significance for replacement of polar aprotic solvents (PAS) 31 5 Conclusions 36 6 Results of external survey 37 Acknowledgements 39 References 40 © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research 5 1 Introduction In 2014 Wageningen Food & Biobased Research conducted a quick-scan for the Dutch National Institute for Public Health and the Environment (RIVM) with the aim to identify potential biobased alternatives to substances of very high concern (SVHC). The report concluded that the substance class of polar aprotic solvents (PAS) was of special interest. These solvents, more specifically NMP (N-methyl pyrolidone), DMAc (dimethylacetamide) and DMF (dimethylformamide), are suspected reprotoxic and are under increasing regulatory pressure. While biobased chemicals offer potential alternatives (given the highly polar character of many biobased feedstocks like carbohydrates), there were also concerns that short term restriction of the use of NMP, DMF and DMAc could be prohibitive to the development of a biobased economy. Since most biobased feedstocks and chemicals contain significantly more oxygen (and water) than their petrochemical counterparts, common industrial petrochemical processes based on distillation and high temperature gas phase reactions are not feasible, due to too high boiling points and thermal instability. Hence, more often solvents need to be used for biomass pretreatment and downstream chemical conversions. Whereas water and alcohols are highly preferred from an environmental and safety point of view, also the use of PAS is often required. Hence, in the first part of the project ‘Verkenning aprotische oplosmiddelen’ emphasis was placed on identifying whether short term restrictions in the use of NMP, DMF and DMAc would have detrimental effects on the development of biomass pretreatment processes. The conclusions from this first part were that this is not the case, due to the large scale of these processes and the (too) high costs associated with the use of non-aqueous solvents. The goal of the second part of the project is to identify new biobased alternatives to the currently disputed PAS by means of a desk study. The first objective of this desk study is to present an overview of both emerging and existing biobased chemicals (and materials), and to identify potential (side) streams of ‘new’ biobased chemicals that will (need to) be valorised in the near future. The description ‘new’ biobased chemicals relates to the fact that these substances are not (yet) commercially available in significant quantities, despite the fact that many of them have been known for more than a century. For example, substances like ethanol, lactic acid and citric acid are not considered new as they are already produced by industrial scale fermentation for a long time. Furthermore, chemicals like bio-succinic acid are not considered new, as they are currently still mostly produced from petrochemical feedstocks. Examples of substances that are considered as new in this study are for instance furandicarboxylic acid (FDCA), levulinic acid and itaconic acid. Another reason to focus on new biobased solvents is that most of the existing biobased solvents (unique or drop-in) such as ethanol, ethyl acetate, or ethyl lactate are unsuitable as functional alternatives to NMP, DMAc and DMF in the majority of their applications. 6 © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research The second objective of this study is to evaluate the replacement potential of these new biobased substances with regard to NMP, DMAc and DMF. Since many biobased chemicals are (highly) polar, the increasing availability of ‘new’ substances with unique chemical structures and properties could be the solution to finding safe alternatives to disputed PAS. © Wageningen Food & Biobased Research, institute within the legal entity Stichting Wageningen Research 7 2 Methods & Terminology For this report use has been made of several literature search
Recommended publications
  • (12) United States Patent (10) Patent No.: US 9.285,681 B2 Hsieh (45) Date of Patent: Mar
    USOO9285681 B2 (12) United States Patent (10) Patent No.: US 9.285,681 B2 Hsieh (45) Date of Patent: Mar. 15, 2016 (54) PHOTOSENSITIVE RESIN COMPOSITION WO WO-2009,133843 A1 * 11, 2009 AND USES THEREOF WO WO 2012, 176694 A1 * 12/2012 WO WO 2013/O12035 A1 * 1, 2013 (71) Applicant: CHI MEI CORPORATION, Tainan OTHER PUBLICATIONS (TW) "Aliphatic compounds” IUPAC Compendium of Chemical Terminol ogy one page from PAC, 1995, 67. 1307 (GLossary of class names of (72) Inventor: Li-Ting Hsieh, Tainan (TW) organic compounds and reactivity intermediates base on structure (IUPAC Recommendations 1995)) onpage 1313, obtained online (73) Assignee: CHI MEI CORPORATION, Tainan from IUPAC gold book.* (TW) CAS Registry No. 215806-04-5, one page obtained from SciFinder database on Mar. 31, 2015 idenying O 1382 as a trade name of this (*) Notice: Subject to any disclaimer, the term of this compound, American Chemical Society copyright. patent is extended or adjusted under 35 English translation of WO 2009 133843 A1 published Nov. 5, 2009, Translation from ProQuest Dialog online done Mar. 30, 2015, 75 U.S.C. 154(b) by 0 days. pages. SciFinder database entry for WO2009 133843 and the list of sub (21) Appl. No.: 14/281,715 stances identified therewith down loaged Apr. 1, 2013, 10 pages.* Derwent-ACC-No. 2009-R51511, English abstract of WO (22) Filed: May 19, 2014 2009 133843 A1 publication dated Nov. 5, 2009 (in same family as TW 201005019 A cited by applicants), Derwent Week: 201265, 6 (65) Prior Publication Data pages down loaded Apr. 1, 2015.* CAS Registry No.
    [Show full text]
  • United States Patent Office Patented Oct
    2,907,745 United States Patent Office Patented Oct. 6, 1959 2 structural strength and, therefore, useful in load-bearing . 2,907,745. applications. POEYURETHANE OF A POLYISOCYANATE, AN Fhese and other objects are accomplished by the present - ACTIVE HYDROGEN COMPOUND, ANEDA HY invention which contemplates the reaction of a substantial DROXYARYL, ALEPHATIC ACID 5 amount of an isocyanate or isothiocyanate, at least half of which must contain two or more isocyanate or isothio Sylvan O. Greenlee, Racine, Wis, assignor to cyanate groups per molecule, with an aliphatic acid, hav S. C. Johnson & Son, Inc., Racine, Wis. ing a total of at least five carbon atoms with a single No. Drawing. Application January 16, 1957 carbon atom being substituted with two hydroxyaryl 0. groups; and an organic compound having an active hy Seria No. 634,411 drogen groups at least two of the following radicals: 7 Claims. (C. 260-47) YH, CYYH, NH, and CYNH, where Y is oxygen or sulfur, which compound is free of other reactive groups. This invention relates to novel resinous compositions It has been found that the addition of hydroxyaryl of matter of the polyurethane type and is directed more 5 aliphatic acids to a polyisocyanate-active hydrogen com particularly to synthetic resinous compositions derived pound reaction mixture is: an unusually advantageous from the reaction of hydroxyaryl aliphatic acids with measure for obtaining polymeric resinous compositions polyisocyanates in presence of an organic compound characterized by excellent protective coating and adhesive capable of entering into the reaction and exerting an in properties when used as a film, and high structural strength fluence upon the nature of the resulting product.
    [Show full text]
  • Diphenolic Acid 126-00-1
    Diphenoilc acid 126-00-1 SUMMARY OF DATA FOR CHEMICAL SELECTION Diphenolic Acid 126-00-1 BASIS OF NOMINATION TO THE CSWG Diphenolic acid is brought to the attention of the CSWG because a new, cost effective manufacturing process is expected to make this chemical an attractive substitute for bisphenol A. Since diphenolic acid is a close structural analog of bisphenol A, environmental releases and consumer exposures from use in baby bottles, dental resins, and lacquers to coat food cans would be similar to those for bisphenol A. Very little information on the toxicity of diphenolic acid was found in the available literature. The chronic effects of diphenolic acid are not well characterized. INPUT FROM GOVERNMENT AGENCIES/INDUSTRY Dr. John Walker, Executive Director of the TSCA Interagency Testing Committee (ITC), Environmental Protection Agency (EPA), provided information on the annual production range of levulinic acid, the precursor chemical of diphenolic acid. Diphenoilc acid 126-00-1 SELECTION STATUS ACTION BY CSWG: 9/28/00 Studies requested: Subchronic (90-day) tests Battery of genetic toxicity tests Priority: High Rationale/Remarks: Presently a medium production volume chemical (<1 million lb/yr) A new manufacturing process is expected to greatly reduce the cost of producing diphenolic acid, thus increasing its use. Potential substitute for bisphenol A Virtually no information on toxicity of diphenolic acid CSWG, through NCI, will alert the EPA’s endocrine disruption program about the need for testing diphenolic acid because of its structural similarity to bisphenol A. NCI will conduct Ames and mouse lymphoma assays. Diphenoilc acid 126-00-1 CHEMICAL IDENTIFICATION CAS Registry Number: 126-00-1 Chemical Abstracts Service Name: Benzenebutanoic acid, 4-hydroxy-γ-(4-hydroxy- phenyl)-γ-methyl- (9CI); valeric acid, 4,4-bis(p- hydroxyphenyl)-(8CI) Synonyms: 4,4-Bis(4-hydroxyphenyl)pentanoic acid; CTFA 00879; diphenolic acid; DPA Structural Class: Phenol Structure, Molecular Formula and Molecular Weight: COOH H3C HO OH C17H18O4 Mol.
    [Show full text]
  • IAEA TECDOC SERIES Radiation Radiation Treatment of Wastewater for Reuse with Particular Focus on Wastewaters Containing Organic Pollutants
    IAEA-TECDOC-1855 IAEA-TECDOC-1855 IAEA TECDOC SERIES Radiation Treatment of Wastewater for Reuse with Particular Focus on Wastewaters Containing Organic Pollutants Wastewaters on Focus for Reuse with Particular Wastewater of Treatment Radiation IAEA-TECDOC-1855 Radiation Treatment of Wastewater for Reuse with Particular Focus on Wastewaters Containing Organic Pollutants International Atomic Energy Agency Vienna ISBN 978–92–0–107818–6 ISSN 1011–4289 @ RADIATION TREATMENT OF WASTEWATER FOR REUSE WITH PARTICULAR FOCUS ON WASTEWATERS CONTAINING ORGANIC POLLUTANTS The following States are Members of the International Atomic Energy Agency: AFGHANISTAN GERMANY PALAU ALBANIA GHANA PANAMA ALGERIA GREECE PAPUA NEW GUINEA ANGOLA GRENADA PARAGUAY ANTIGUA AND BARBUDA GUATEMALA PERU ARGENTINA GUYANA PHILIPPINES ARMENIA HAITI POLAND AUSTRALIA HOLY SEE PORTUGAL AUSTRIA HONDURAS QATAR AZERBAIJAN HUNGARY REPUBLIC OF MOLDOVA BAHAMAS ICELAND ROMANIA BAHRAIN INDIA BANGLADESH INDONESIA RUSSIAN FEDERATION BARBADOS IRAN, ISLAMIC REPUBLIC OF RWANDA BELARUS IRAQ SAINT VINCENT AND BELGIUM IRELAND THE GRENADINES BELIZE ISRAEL SAN MARINO BENIN ITALY SAUDI ARABIA BOLIVIA, PLURINATIONAL JAMAICA SENEGAL STATE OF JAPAN SERBIA BOSNIA AND HERZEGOVINA JORDAN SEYCHELLES BOTSWANA KAZAKHSTAN SIERRA LEONE BRAZIL KENYA SINGAPORE BRUNEI DARUSSALAM KOREA, REPUBLIC OF SLOVAKIA BULGARIA KUWAIT SLOVENIA BURKINA FASO KYRGYZSTAN SOUTH AFRICA BURUNDI LAO PEOPLE’S DEMOCRATIC SPAIN CAMBODIA REPUBLIC SRI LANKA CAMEROON LATVIA SUDAN CANADA LEBANON SWEDEN CENTRAL AFRICAN LESOTHO SWITZERLAND
    [Show full text]
  • Production of Levulinic Acid and Use As a Platform Chemical for Derived Products
    Production of Levulinic Acid and Use as a Platform Chemical for Derived Products JJ Bozell* and L. Moens, National Renewable Energy Laboratory D. C. Elliott, Y Wang, G. G. Neuenscwander, Pacific Northwest National Laboratory S. W Fitzpatrick, Biofine, Inc. R. J. Bilski, Chemical Industry Services, Inc. J. L. Jarnefeld, New York State Energy Research andDevelopmentAuthority ABSTRACT Levulinic acid (LA) can be produced cost effectively and in high yield from renewable feedstocks in a new industrial process. The technology is being demonstrated on a one ton/day scale at a facility in South Glens Falls, New York. Low cost LA can be used as a platform chemical for the production ofa wide range ofvalue-added products. This research has demonstrated that LA can be converted to methyltetrahydrofuran (MTHF), a solvent and fuel extender. MTHF is produced in >80% molar yield via a single stage catalytic hydrogenation process. A new preparation of 0­ aminolevulinic acid (DALA), a broad spectrum herbicide, from LA has also been developed. Each step in this new process proceeds in high (>80%) yield and affords DALA (as the hydrochloride salt) in greater than 90% purity, giving a process that could be commercially viable. LA is also being investigated as a starting material for the production of diphenolic acid (DPA), a direct replacement for bisphenol A. Introduction Biomass can be used as a raw material to produce large numbers of chemicals, each with the potential to be as fundamental to the chemical industry as methane or BTX. Yet, to date, many ofthese products have failed in the marketplace because they do not pass the most practical test ofmarket viability: is the product available at a low enough cost to use as a chemicalproduct or intermediate? Levulinic acid ( LA, 4-oxopentanoic acid), has frequently been proposed as such a building block.
    [Show full text]
  • WO 2010/068673 Al
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 17 June 2010 (17.06.2010) WO 2010/068673 Al (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C09D 167/00 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (21) International Application Number: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, PCT/US2009/067347 DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 9 December 2009 (09.12.2009) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, (25) Filing Language: English NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, (26) Publication Language: English SE, SG, SK, SL, SM, ST, SV, SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 61/121,454 10 December 2008 (10.12.2008) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, VALSPAR SOURCING, INC. [US/US]; PO Box 1461, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, Minneapolis, MN 55440-1461 (US).
    [Show full text]
  • Attempts Towards the Catalytic Ketonization of Levulinic Acid to 2,5,8- Nonanetrione
    Attempts towards the Catalytic Ketonization of Levulinic Acid to 2,5,8- nonanetrione by Igor Tadeu da Cunha A Thesis presented to The University of Guelph In partial fulfilment of requirements for the degree of Master of Science in Chemistry Guelph, Ontario, Canada © Igor Tadeu da Cunha, April, 2018 ABSTRACT ATTEMPTS TOWARDS THE CATALYTIC KETONIZATION OF LEVULINIC ACID TO 2,5,8-NONANETRIONE Igor Tadeu da Cunha Advisor: University of Guelph, 2018 Dr. Marcel Schlaf The ketonization of carboxylic acids to ketones has been explored since the mid 1800’s. However, the vast majority of studies focus on the use of carboxylic acids that do not possess any additional functional groups. Levulinic acid (LA), an important biomass derived platform chemical, presents both a carboxylic acid and a ketone functionality, which considerably increases the self-reactivity of this molecule. This is especially apparent at the high temperatures (300-400 °C) required for ketonizations over solid catalysts like CeO2/Al2O3 or ZrO2. The primary product of the ketonization of LA would be 2,5,8-nonanetrione (NTO) – which due to its structure – could be hydrogenated to the corresponding triol and applied as a 3D-crosslinker in the polymer industry. Prior attempts to produce this molecule required very complex synthetic routes and processes that could not be applied on industrial scale. Our goal was to develop a fixed-bed flow reactor that would promote the ketonization of LA in a one-step process; however, all attempts to obtain NTO in useful yields resulted in the formation of angelica lactones – the products of the self-reaction of LA – and 3-methyl-2-cyclopenten-1-one (3-MCP) which is the product of self-aldol condensation of the transient NTO, followed by further elimination of H2O and acetone.
    [Show full text]
  • Top Value Added Chemicals from Biomass Volume I—Results of Screening for Potential Candidates from Sugars and Synthesis Gas
    U.S. Department of Energy Energy Efficiency and Renewable Energy Bringing you a prosperous future where energy is clean, abundant, reliable, and affordable Top Value Added Chemicals from Biomass Volume I—Results of Screening for Potential Candidates from Sugars and Synthesis Gas Produced by the Staff at Pacific Northwest National Laboratory (PNNL) National Renewable Energy Laboratory (NREL) Office of Biomass Program (EERE) For the Office of the Biomass Program T. Werpy and G. Petersen, Editors National Renewable Energy Laboratory Top Value Added Chemicals From Biomass Volume I: Results of Screening for Potential Candidates from Sugars and Synthesis Gas Produced by Staff at the Pacific Northwest National Laboratory (PNNL) and the National Renewable Energy Laboratory (NREL) T. Werpy and G. Petersen, Principal Investigators Contributing authors: A. Aden and J. Bozell (NREL); J. Holladay and J. White (PNNL); and Amy Manheim (DOE-HQ) Other Contributions (research, models, databases, editing): D. Elliot, L. Lasure, S. Jones and M. Gerber (PNNL); K. Ibsen, L. Lumberg and S. Kelley (NREL) August 2004 Acknowledgement: The authors gratefully acknowledge the support and assistance from NREL staff members S. Bower, E. Jarvis, M. Ruth, and A. Singh and review by Paul Stone and Mehmet Gencer, independent consultants from the chemical industry as well as specific input and reviews on portions of the report by T. Eggeman of Neoterics International and Brian Davison of Oak Ridge National Laboratory. NOTICE This report was prepared as an account of work sponsored by an agency of the United States government. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights.
    [Show full text]
  • New Frontiers in the Catalytic Synthesis of Levulinic Acid: from Sugars to Raw and Waste Biomass As Starting Feedstock
    catalysts Review New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock Claudia Antonetti, Domenico Licursi, Sara Fulignati, Giorgio Valentini and Anna Maria Raspolli Galletti * Department of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi, 13, 56124 Pisa, Italy; [email protected] (C.A.); [email protected] (D.L.); [email protected] (S.F.); [email protected] (G.V.) * Correspondence: [email protected]; Tel.: +39-050-2219290 Academic Editor: Keith Hohn Received: 28 October 2016; Accepted: 1 December 2016; Published: 6 December 2016 Abstract: Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance and environmentally benign nature. The LA transition from niche product to mass-produced chemical, however, requires its production from sustainable biomass feedstocks at low costs, adopting environment-friendly techniques. This review is an up-to-date discussion of the literature on the several catalytic systems that have been developed to produce LA from the different substrates. Special attention has been paid to the recent advancements on starting materials, moving from simple sugars to raw and waste biomasses. This aspect is of paramount importance from a sustainability point of view, transforming wastes needing to be disposed into starting materials for value-added products. This review also discusses the strategies to exploit the solid residues always obtained in the LA production processes, in order to attain a circular economy approach.
    [Show full text]
  • Chemicals Purported to Be Endocrine Disrupters
    Chemicals purported to be endocrine disrupters A compilation of published lists INCLUSION OF A PARTICULAR SUBSTANCE IN THIS REPORT SHOULD NOT BE TAKEN TO CONSTITUTE ANY ENDORSEMENT OF ITS STATUS AS A PROVEN OR POTENTIAL ENDOCRINE DISRUPTING OR MODIFYING AGENT BY EITHER IEH OR DEFRA IEH Web Report W20 MARCH 2005 The Institute for Environment and Health was established by the Medical Research Council at the University of Leicester in 1993. The Institute is principally funded by UK Government Departments and Agencies by way of specific research and consultancy contracts. This report was prepared by the MRC Institute for Environment and Health for the Department for Environment, Food and Rural Affairs and issued in June 2002. The views expressed here do not necessarily represent those of any Government Department or Agency. Written by C Botham and P Holmes Reviewed and edited by P Harrison and E Stutt Web Report edited by J Emeny IEH will continue to make this document available at this Web site (or by a link to a different site). Any changes to its contents will be clearly recorded, either by a note of corrigenda or the issue of a new edition, identified by an amended report reference number and date. A copy of this document is also held at the British Lending Library. Please cite as: IEH (2005) Chemicals Purported to be Endocrine Disrupters: A Compilation of Published Lists (Web Report W20), Leicester, UK, MRC Institute for Environment and Health, available at http://www.le.ac.uk/ieh/ ©Institute for Environment and Health, 2005 ISBN 1 899110
    [Show full text]
  • United States Patent (19 11) 4,236,021 Hsu Et Al
    United States Patent (19 11) 4,236,021 Hsu et al. 45 Nov. 25, 1980 (4) EFSETEENSEATURE OF FOREIGN PATENT DOCUMENTS 764364 8/1971 Belgium ............................ 562/577 75) Inventors: Chin C. Hsu, Avon Lake; Dwight W. Primary Examiner-Vivian Garner Chasar, Northfield, both of Ohio Attorney, Agent, dr Firm-Nestor W. Shust (73) Assignee: The B. F. Goodrich Company, Akron, (57) ABSTRACT Ohio An improved process for the manufacture of levulinic acid which comprises esterification of furfuryl alcohol 21 Appl. No.: 36,718 in the presence of a different alcohol selected from 1a. unsubstituted primary and secondary carbon-chain or 22 Filed: May 7, 1979 carbon-ring alcohols containing 1 to 10 carbon atoms in 51) Int, C1.3 COTC 67/00; CO7C 69/716; the presence of a small amount of acid as a catalyst, Yaak po e o 0 e ovo as as was a C07C 51 05: CO7C 59/185 purification of the resulting levulinate ester by vacuum (52) U.S. Cl 560/174; 203/57 distillation of a mixture of the levulinate ester and a high is us....................203/60.266/347 562757 boiling solvent and hydrolysis of the purified levulinate (58) Field of Search 560774. 562/577, ester in the presence of water and a small amount of . or room. 303/57 66 strong acid catalyst to yield levulinic acid-water mix y ture. The improvement resides in the purification being 56 References Cited carried out prior to hydrolysis and in using a high boil ing solvent in the purification step to prevent the forma U.S.
    [Show full text]
  • Synthesis of Eugenol-Based Silicon-Containing Benzoxazines and Their Applications As Bio-Based Organic Coatings
    coatings Article Synthesis of Eugenol-Based Silicon-Containing Benzoxazines and Their Applications as Bio-Based Organic Coatings Jinyue Dai 1,2,3, Shimin Yang 4, Na Teng 1,3, Yuan Liu 1,2,5, Xiaoqing Liu 1,3,*, Jin Zhu 1,3 and Jun Zhao 4 1 Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China; [email protected] (J.D.); [email protected] (N.T.); [email protected] (Y.L.); [email protected] (J.Z.) 2 University of Chinese Academy of Sciences, Beijing 100049, China 3 Key Laboratory of Bio-based Polymeric Materials Technology and Application of Zhejiang Province, Ningbo 315201, China 4 Shanghai Space Propulsion Technology Research Institute, Shanghai 201100, China; [email protected] (S.Y.); [email protected] (J.Z.) 5 Engineering Research Center for Materials Protection of Wear and Corrosion of Guizhou Province, Guiyang University, Guiyang 550005, China * Correspondence: [email protected] Received: 9 January 2018; Accepted: 21 February 2018; Published: 27 February 2018 Abstract: In this work, several bio-based main-chain type benzoxazine oligomers (MCBO) were synthesized from eugenol derivatives via polycondensation reaction with paraformaldehyde and different diamine. Afterwards, their chemical structures were confirmed by Fourier Transform Infrared Spectroscopy (FT-IR) and Nuclear Magnetic Resonance Spectroscopy (1H-NMR). The curing reaction was monitored by Differential Scanning Calorimetry (DSC) and FT-IR. The polybenzoxazine films were prepared via thermal ring-opening reaction of benzoxazine groups without solvent, and their thermodynamic properties, thermal stability, and coating properties were investigated in detail. Results indicated that the cured films exhibited good thermal stability and mechanical properties, ◦ showing 10% thermal weight loss (Td10%) temperature as high as 408 C and modulus at a room temperature of 2100 MPa as well as the glass transition temperature of 123 ◦C.
    [Show full text]